Care and/or make-up cosmetic composition structured with silicone polymers

ABSTRACT

Care and/or make-up cosmetic composition comprising: a liquid continuous fatty Phase structured with at least one structuring polymer (homopolymer or copolymer) having a weight-average molecular mass ranging from 500 to 500 000, containing at least one moiety comprising: at least one polyorganosiloxane group consisting of 1 to 1 000 organosiloxane units in the chain of the moiety or in the form of a graft, and at least two groups capable of establishing hydrogen interactions, Chosen from ester, amide, sulphonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof, the polymer being solid at room temperature and soluble in the liquid fatty Phase at a temperature of 25 to 250° C., the Said liquid fatty Phase comprising at least one compound capable of reducing the enthalpy of fusion of the structuring polymer, and then the liquid fatty Phase, the structuring polymer and the compound capable of reducing the enthalpy of fusion of the structuring polymer forming a physiologically acceptable medium.

TECHNICAL FIELD

The present invention relates to a care and/or make-up cosmeticcomposition for the skin, including the hair, and/or the lips of humanbeings, containing a liquid fatty phase comprising at least one oil,structured with a particular polymer, provided in particular in the formof a cast make-up product, in particular as a make-up stick or dome suchas lipsticks, whose application is easy and leads to a substantial,especially coloured, glossy and non-migrating deposit.

A care cosmetic composition is a composition which comprises at leastone active compound for, for example, treating wrinkles, formoisturizing the skin and the lips, for protecting the skin, the lipsand superficial body growths from ultraviolet rays, for treating acneand/or for acting as self-tanning agent.

The invention relates more particularly to cosmetic and dermatologicalcompositions such as make-up products for easy application and leadingto a large deposit and exhibiting properties of staying power, but alsoof non-transfer and stability.

PRIOR STATE OF THE ART

In cosmetic products, it is common to find a structured, namely gelledand/or rigidified, liquid fatty phase. A composition is rigidified inparticular in the case of solid compositions such as balms andlipsticks, eyeshadows, concealer products and foundations which havebeen cast. This structuring is obtained with the aid of waxes orfillers. Unfortunately, these waxes and fillers tend to mattify thecomposition; which is not always desirable in particular for a lipstickor an eyeshadow.

The expression liquid fatty phase is understood to mean, for thepurposes of the application, a fatty phase which is liquid at roomtemperature (25° C.) and atmospheric pressure (760 mmHg), which iscomposed of one or more fatty substances which are liquid at roomtemperature, which are also called oils, which are compatible with eachother.

The expression structured liquid phase is understood to mean arigidified or gelled liquid fatty phase.

The expression rigified liquid fatty phase is understood to mean, forthe purposes of the application, that this rigified phase does not rununder its own weight when a silicone polyamide is added thereto.

The expression gelled liquid phase for the purposes of the applicationis understood to mean that the viscosity of this phase is increasedbecause of the addition of a silicone polyamide to this fatty phase.

The structuring of the liquid fatty phase makes it possible inparticular to limit its exudation from solid compositions and,furthermore, to limit, after deposition on the skin or the lips, themigration of this phase into wrinkles and fine lines, which isparticularly sought for a lipstick or an eyeshadow. The expressionmigration is understood to mean an overflowing of the compositiondeposited on the skin or the lips, outside its initial outline.

The gloss is mainly linked to the nature of the liquid fatty phase.Thus, it is possible to reduce the amount of waxes and fillers in thecomposition in order to increase the gloss of a lipstick, but then themigration of the liquid fatty phase increases. In other words, theamounts of waxes and fillers necessary for producing a stick of suitablehardness are a barrier to the gloss of the deposit.

The document EP-A-1 068 856 [1] describes solid cosmetic compositions,with no wax, containing a liquid fatty phase structured with a polymer,in which the fatty phase is mainly a non-silicone oil.

The document WO-A-01/97758 [2] describes cosmetic compositions based onpolyamide resins comprising a structuring agent chosen from esters andamides of N-acylamino acids and mixtures thereof. The composition alsocomprises a solvent for the polyamide resin which may be chosen fromunsaturated and saturated fatty alcohols, fatty and/or aromaticcarboxylic acid esters, ethoxylated and/or propoxylated alcohols andacids, silicones, mineral oils and branched-chain hydrocarbons;preferably, fatty acid esters, fatty alcohols, mineral oils, branchedhydrocarbons and mixtures thereof.

The use of fatty phases based on silicone oils makes it possiblecurrently to obtain cosmetic compositions having a long staying powerwhen the oils are only slightly volatile or are non-volatile, namely agood staying power in particular of the colour over time (unchanging,unfading), and transfer-free compositions when the silicone oils arevolatile, not forming a deposit on a support such as a glass, a cup, afabric or a cigarette, placed in contact with the film of make-up.

Currently, the use of silicone oils in cosmetics is limited by the smallnumber of molecules which can gel these media and thus give compositionswhich exist in solid form such as lipsticks or cast foundations forexample. The use of cosmetic compositions whose fatty phase ispredominantly siliconized leads, in most cases, to problems ofcompatibility with the ingredients conventionally used in cosmetics.

In the documents U.S. Pat. No. 5,874,069 [3], U.S. Pat. No. 5,919,441[4], U.S. Pat. No. 6,051,216 [5], WO-A-02/17870 [6], and WO-A-02/17871[7], WO-A-99/06473 [12], U.S. Pat. No. 6,353,076 [13], cosmeticcompositions such as deodorant sticks or gels, comprising a siliconeoily phase gelled with a polysiloxane- and polyamide-based wax, or witha polymer containing siloxane groups and groups capable of hydrogeninteractions, have been prepared.

In WO-A-02/17870 [6], it is envisaged to add to the composition anotherstructuring agent, but the quantities added should be low, for exampleless than 0.5% in the case of hydroxystearic acid, in order to preservethe clarity of the product.

In WO-A-02/17871 [7], it is also envisaged to use a second structuringagent with the silicone polymer in a quantity representing 0.5 to 2% byweight of the composition, and a solvent system comprising anon-silicone organic compound, a volatile silicone and optionallyanother silicone.

The document EP-A-1 177 784 [8] illustrates a deodorant compositioncomprising a liquid phase containing, for example, a volatile siliconeand optionally a non-volatile silicone and/or a non-silicone hydrophobicorganic liquid, structured with an organic compound with amido groups,with optionally one or more polymeric or non-polymeric secondarystructuring agents in small proportions. Among the secondary structuringagents, this document mentions polymers having siloxane groups andgroups exhibiting hydrogen interactions without giving examples orresults on a composition using these polymers.

The sticks obtained by structuring the liquid fatty phase with solelyone or more gelling silicone polymers do not exhibit sufficientmechanical resistance to shearing, in particular during the applicationof the stick to the lips and/or the skin, leading to breaking of thestick.

It is evident from the above that the formulation of polymers such assilicone polyamides (PASi) in compatible fatty media makes it possibleto obtain solid make-up systems not requiring the use of waxes, and inparticular the structuring of highly, or even completely siliconizedsystems, which is normally difficult to obtain with wax-type traditionalstructuring agents.

However, it has been possible to demonstrate that the application of theformulas thus obtained could be difficult and that the deposit was notobtained in a sufficient quantity to allow the making up.

The application and the deposit are all the less satisfactory as theconcentration required for obtaining a solid system of sufficienthardness is high.

DISCLOSURE OF THE INVENTION

The aim of the invention is precisely to provide a care or make-upcomposition for the skin and/or the lips, which makes it possible toovercome the disadvantages and to solve the problems mentioned above. Inparticular, the aim of the invention is to provide a composition whoseapplication is easy and leads to a large deposit, that is to say a largemass, in any case larger than with prior art compositions. The largerdeposit of material gives more “make-up effect”, and in particular inthe case of pigmented, coloured compositions, the deposit having a moreintense colour allows the making up, for example, of the lips.

Surprisingly, the applicant has found that the use of particularpolymers combined with one or more compositions capable of reducing theenthalpy of fusion and possibly the melting temperature of thesepolymers made it possible to structure, in the absence or in thepresence of small quantities of wax, the liquid fatty phases, based onsilicone oil for example, in the form of a make-up or care product whoseapplication was easy, with in particular excellent slipperiness duringapplication and that this use led to a large deposit, that is to say alarge mass, in any case larger than with prior art compositions. Thelarger deposit of composition gives more “make-up effect”, and inparticular in the case of pigmented, coloured compositions, the deposithaving a more intense colour allows the making up, for example, of thelips, a making up which was not satisfactorily possible or even not atall possible with the prior art compositions.

It was additionally noted, equally surprisingly, that the compositionsof the invention, including the combinations cited above, exhibitedimproved gloss both as regards the product before application and thedeposit, if this property is desired. Furthermore, the compositionsaccording to the invention, including the combinations cited above, givea non-migrating film or deposit, which has enhanced properties ofstaying power, and possibly of non-transfer and which is not sticky tothe touch.

The combination of these particular compounds with one or more compoundscapable of reducing their enthalpy of fusion ΔH and optionally theirmelting temperature m.p. makes it possible to obtain gels, in particularsolid gels, having a good mechanical strength and an acceptable rheologyin order to allow a deposit with a large mass, sufficient to allow themake-up, which additionally has an improved gloss.

Make-up or care cosmetic compositions comprising the combination of aparticular polymer according to the invention and a specific compoundwhich is a compound capable of lowering, reducing the enthalpy ΔH andoptionally the melting temperature m.p. of the polymer are not describedin the prior art.

The effects obtained by virtue of this combination of a particularpolymer and a particular compound capable of reducing the enthalpy offusion and optionally of reducing the melting point of the polymer, inparticular the surprising improvement of the ease of application, of thedeposited mass, as well as the gloss of the deposit and of the product,do not appear in the prior art documents.

The invention not only applies to make-up products for the lips such aslipsticks, lip pencils and lip glosses, but also to care products forthe skin, including the scalp, and the lips, such as sun protectionproducts in stick form for the skin, the face or the lips, or lip balms,to make-up products for the skin, both of the face and of the humanbody, such as foundations cast as a stick or in a dish, concealerproducts and temporary tattoo products, to cleansing products, inparticular in stick form, and to make-up products for the eyes such aseyeliners, in particular in pencil form, and mascaras, in particularcakes for keratinous fibres (eyelashes, eyebrows, hair).

More precisely, the subject of the invention is a make-up cosmeticcomposition comprising: a liquid continuous fatty phase structured withat least one structuring polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions, chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,    -   the polymer being solid at room temperature and soluble in the        liquid fatty phase at a temperature of 25 to 250° C.,

the said liquid fatty phase comprising at least one compound capable ofreducing the enthalpy of fusion of the structuring polymer,

the said composition containing at least one pigment, and

the liquid fatty phase, the structuring polymer and the compound capableof reducing the enthalpy of fusion of the structuring polymer forming aphysiologically acceptable medium.

According to the invention, the expression “structuring polymer” isgenerally understood to mean a polymer which makes it possible torigidify or to gel the composition by forming hydrogen bonds.

The composition of the invention may be provided in the form of a paste,a solid or a more or less viscous cream. It may be a simple or multiple,in particular an oil-in-water or water-in-oil, water-in-oil-in-water oroil-in-water-in-oil emulsion, or a rigid or soft gel having an oilycontinuous phase. The simple or multiple emulsion may comprise anaqueous or oily continuous phase optionally containing dispersed lipidvesicles. In particular, it is provided in a form cast as a stick or ina dish and more especially in the form of an oily, in particularanhydrous, rigid gel and in particular of an anhydrous stick. Moreespecially, it is provided in the form of a translucent or opaque rigidgel (according to whether it contains pigments or otherwise), the liquidfatty phase forming the continuous phase. An anhydrous composition willcomprise less than 10% by weight of water, for example less than 5% byweight, preferably less than 2% by weight of water.

The structuring of the liquid fatty phase can be modulated according tothe nature of the structuring polymer and of the compound capable ofreducing the enthalpy and possibly the melting temperature used, and maybe such that a rigid structure is obtained in the form of a baton, astick or a dome, having good mechanical strength and already having aglossy appearance. Especially when they are coloured, these batons makeit possible, after easy application, to obtain a glossy deposit, whichis in particular coloured, with a large mass, which does not migrate andwhich has good staying power, in particular of the colour over time. Thecomposition may comprise one or more structuring polymers and one ormore compounds which reduce the enthalpy of fusion and optionally themelting temperature of these polymers.

Avantageously, the composition of the invention is a composition for thelips and even better a lipstick composition in particular in stick form.

Liquid Fatty Phase

The liquid fatty phase according to the invention comprises at least oneoil generally chosen from hydrocarbon, silicone and fluorinated oils.

An oil is a non-aqueous compound which is immiscible with water.

The liquid fatty phase may comprise at least one volatile oil.

For the purposes of the invention, a volatile oil-advantageously has aflash point preferably of 35 to 135° C. (measured according to themethod) or no flash point. The flash point is the temperature at whichthe vapours emitted by a fuel ignite upon contact with a flame, a sparkor a heat source.

Volatile oils advantageously have at room temperature (25° C.) andatmospheric pressure (760 mmHg) a vapour pressure ranging from 0.01 mmto 300 mmHg (1.33 Pa to 40 000 Pa) and even better ranging from 0.05 to190 mmHg (6.65 Pa to 25 330 Pa).

According to the invention, the volatile oil may be chosen from linear,branched or cyclic silicone oils having a flash point equal to orgreater than 40° C. and advantageously greater than the softening pointof the gelling system and/or a viscosity of less than 8 cSt, such aslinear, branched or cyclic polydimethylsiloxanes (PDMS) having from 3 to7 silicon atoms.

By way of examples of volatile oils, there may be mentioned thecompounds given in Table 1 below.

The composition may contain a non-volatile silicone oil.

The silicone oils of the invention have a viscosity which isadvantageously chosen from the range going from 5 to 800 000 cSt at 25°C., preferably from 10 to 500 000 cSt, and even better from 10 to 5 000cSt.

The non-volatile silicone oils may be polydimethylsiloxanes,polyalkylmethylsiloxanes, dimethicone copolyols, alkylmethiconecopolyols, cetyldimethicone, silicones with alkylglyceryl ether groups,silicones with side amine groups and dilauroyltrimethylol propanesiloxysilicate. The alkyl groups of these oils have in particular from 2to 24 carbon atoms.

The non-volatile silicone oils which can be used in the invention may bein particular linear, non-volatile polydimethylsiloxanes (PDMS) whichare liquid at room temperature; polydimethylsiloxanes containing alkyl,alkoxy or phenyl groups, which are pendent and/or at the silicone chainend, groups each having from 2 to 24 carbon atoms; phenylated siliconessuch as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyldimethicones,diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, fluorinated silicones with one or moregroup(s) that is (are) pendent or at the chain end having from 1 to 12carbon atoms of which all or some of the hydrogen atoms are substitutedwith fluorine atoms, dimethiconols and mixtures thereof.

TABLE 1 Flash point Viscosity Compound (° C.) (cSt) Octyltrimethicone 931.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2(cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane 55 2.5(cyclotetradimethylsiloxane or D4) Dodecamethylcyclohexasiloxane (D6) 937 Decamethyltetrasiloxane (L4) 63 1.7 KF 96 A from Shin Etsu 94 6 PDMS(polydimethylsiloxane) DC 200 56 1.5 (1.5 cSt) from Dow Corning PDMS DC200 (2 cSt) from Dow 87 2 Corning PDMS DC 200 (5 cSt) 134 5 from DowCorning PDMS DC 200 (3 cSt) 102 3 from Dow Corning

In other words, the volatile silicone oil(s) may be chosen for examplefrom the group consisting of the compounds of Table 1,heptamethyloctyltrisiloxane, dodecamethylpentasiloxane and mixturesthereof.

The volatile silicone oil may also be chosen from the group comprisingfluorinated silicone oils such as silicones with alkyl andperfluoroalkyl groups, silicones with oxyethylenated/oxypropylenated(EO/PP) side groups and with perfluorinated groups, silicones withperfluorinated side groups and with glycerolated side groups,perfluoroalkylmethylphenylsiloxanes, these oils having a vapour pressuregreater than or equal to 0.02 mmHg.

The volatile non-silicone oils may be chosen from the group comprisinghydrocarbon oils and volatile esters and ethers such as volatilehydrocarbons such as isododecane and isohexadecane, C₈-C₁₆ isoparaffins,isohexyl or isodecyl neopentanoates.

The volatile oil may also be chosen from fluorinated oils such asperfluoropolyethers, perfluoroalkanes such as perfluorodecalin,perfluorodamantanes, esters (monoesters, diesters and triesters) ofperfluoroalkyl phosphates and fluorinated ester oils.

By way of example of volatile non-silicone oils which can be used in theinvention, there may be mentioned the compounds of Table 2 whichfollows.

TABLE 2 Flash point Compound (° C.) Isododecane 43 Isohexadecane 102Isodecyl neopentanoate 118 Propylene glycol n-butyl ether 60 Ethyl3-ethoxypropionate 58 Propylene glycol methyl ether 46 acetate* Isopar L(C₁₁–C₁₃ isoparaffin) 62 Isopar H (C₁₁–C₁₂ isoparaffin) 56

The liquid fatty phase advantageously contains at least 30%, and evenbetter at least 40% by weight of silicone oil(s) advantageously having aviscosity of less than 1 000 cSt and even better of less than 100 cStbecause the silicone polymers used in the invention are more soluble insilicone oils of low viscosity. It may also contain other non-siliconeoils or a mixture of non-silicone oils.

When the fatty phase comprises a volatile oil, it advantageouslyrepresents from 3 to 89.4%, and even better from 5 to 60%, for examplefrom 5 to 10% of the total weight of the composition.

The liquid fatty phase may also contain other non-silicone oils, forexample polar oils such as:

hydrocarbonaceous vegetable oils with a high content of triglyceridesconsisting of esters of fatty acids and of glycerol in which the fattyacids may have varied chain lengths, it being possible for the latter tobe linear or branched, saturated or unsaturated; these oils are inparticular wheat germ, maize, sunflower, karite, castor, sweet almond,macadamia, apricot, soybean, rapeseed, cottonseed, lucerne, poppy seed,pumpkin seed, sesame, gourd, avocado, hazelnut, grapeseed orblackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye,safflower, candlenut, passion flower and rose musk oils; ortriglycerides of caprylic/capric acids such as those sold by the companyStearines Dubois or those-sold under the names Miglyol 810, 812 and 818by the company Dynamit Nobel;

synthetic oils or esters of formula R_(a)COOR_(b) in which R_(a)represents the residue of a linear or branched higher fatty acidcontaining from 1 to 4.0 and even better from 7 to 19 carbon atoms andR_(b) represents a branched hydrocarbon chain containing from 1 to 40and even better from 3 to 20 carbon atoms, with R_(a)+R_(b)≧10 such as,for example, Purcellin oil (ketostearyl octanoate), isononylisononanoate, C₁₂ to C₁₅ alcohol benzoate, isopropyl myristate,2-ethylhexyl palmitate, octanoates, decanoates or ricinoleates ofalcohols or of polyalcohols; hydroxylated esters such as isostearyllactate, diisostearyl malate; and esters of pentaerythritol;

synthetic ethers having from 10 to 40 carbon atoms;

fatty acids such as oleic, linoleic or linolenic acid; and

mixtures thereof.

The liquid fatty phase may also contain apolar oils such as linear orbranched hydrocarbons or fluorocarbons of synthetic or mineral origin,which are volatile or not, such as volatile oils of paraffin (such asisoparaffins, isododecane) or non-volatile oils of paraffin and itsderivatives, petroleum jelly, polydecenes, hydrogenated polyisobutenesuch as parleam, squalane, and mixtures thereof.

Thus, the invention may be carried out for example with the followingdifferent fatty phases:

1) a fatty phase consisting of a mixture of oils comprising at least onenonvolatile silicone oil and at least one volatile silicone oil;

2) a fatty phase consisting of a mixture of oils comprising at least onenonvolatile silicone oil and at least one nonsilicone volatile oil;

3) a fatty phase consisting of a mixture of oils comprising at least onenonvolatile silicone oil, at least one volatile silicone oil and atleast one volatile nonsilicone oil;

4) a fatty phase consisting of a mixture of oils comprising at least onevolatile silicone oil, one nonvolatile nonsilicone oil and optionally atleast one volatile nonsilicone oil; and

5) a fatty phase consisting solely of volatile silicone oil(s).

In cases 1), 2) and 3), the mixture may also comprise a nonvolatilenonsilicone oil. It being of course understood that in all cases, and inaccordance with the invention, the fatty phase comprises a compoundcapable of reducing the temperature and the enthalpy of fusion of thestructuring polymer.

Generally, the liquid fatty phase represents from 5 to 99% of the totalweight of the composition and even better from 20 to 75%.

Structuring Silicone Polymer

The structuring polymer(s) of the composition are solid at roomtemperature (25° C.) and atmospheric pressure (760 mmHg) and are solublein the liquid fatty phase at a temperature of 25 to 250° C.

The expression polymer is understood to mean, for the purpose of theinvention, a compound having at least 2 repeating moieties, preferablyat least 3 repeating moieties and even better 10 repeating moieties.

In the composition of the invention, the structuring silicone polymergenerally represents from 0.5 to 80%, preferably from 2 to 60% and evenbetter from 5 to 40% of the total weight of the composition.

Moreover, the polymer of the structuring polymer/oil(s), for examplesilicone oils and other oils, mass ratio is preferably from 0.1 to 50%.

The polymers used as structuring agents in the composition of theinvention are polymers of the polyorganosiloxane type such as thosedescribed in the documents U.S. Pat. No. 5 874 069 [3], U.S. Pat. No.5,919,441 [4], U.S. Pat. No. 6,051,216 [5] and U.S. Pat. No. 5,981,680[11].

According to the invention, the polymers used as structuring agent maybelong to the following two families:

1) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being situated inthe polymer chain; and/or

2) polyorganosiloxanes comprising at least two groups capable ofestablishing hydrogen interactions, these two groups being situated onthe grafts or branches.

The polymers comprising two groups capable of establishing hydrogeninteractions in the polymer chain may be polymers comprising at leastone moiety corresponding to the formula:

in which:

-   -   1) R¹, R², R³ and R⁴, which may be identical or different,        represent a group chosen from:        -   linear, branched or cyclic, saturated or unsaturated, C₁ to            C₄₀ hydrocarbon-based groups, possibly containing in their            chain one or more oxygen, sulphur and/or nitrogen atoms, and            possibly being partially or totally substituted with            fluorine atoms,        -   C₆ to C₁₀ aryl groups, optionally substituted with one or            more C₁ to C₄ alkyl groups,        -   polyorganosiloxane chains possibly containing one or more            oxygen, sulphur and/or nitrogen atoms;    -   2) the groups X, which may be identical or different, represent        a linear or branched C₁ to C₃₀ alkylenediyl group, possibly        containing in its chain one or more oxygen and/or nitrogen        atoms;    -   3) Y is a saturated or unsaturated, C₁ to C₅₀ linear or branched        divalent alkylene, arylene, cycloalkylene, alkylarylene or        arylalkylene group, possibly comprising one or more oxygen,        sulphur and/or nitrogen atoms, and/or bearing as substituent one        of the following atoms or groups of atoms: fluorine, hydroxyl,        C₃ to C₈ cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyl        optionally substituted with 1 to 3 C₁ to C₃ alkyl groups, C₁ to        C₃ hydroxyalkyl and C₁ to C₆ aminoalkyl, or    -   4) Y represents a group corresponding to the formula:

in which

-   -   T represents a linear or branched, saturated or unsaturated, C₃        to C₂₄ trivalent or tetravalent hydrocarbon-based group        optionally substituted with a polyorganosiloxane chain, and        possibly containing one or more atoms chosen from O, N and S, or        T represents a trivalent atom chosen from N, P and Al, and    -   R⁵ represents a linear or branched C₁ to C₅₀ alkyl group or a        polyorganosiloxane chain, possibly comprising one or more ester,        amide, urethane, thiocarbamate, urea, thiourea and/or        sulphonamide groups, which may possibly be linked to another        chain of the polymer;    -   5) the groups G, which may be identical or different, represent        divalent groups chosen from:

in which R⁶ represents a hydrogen atom or a linear or branched C₁ to C₂₀alkyl group, on condition that at least 50% of the groups R⁶ of thepolymer represent a hydrogen atom and that at least two of the groups Gof the polymer are a group other than:

6) n is an integer ranging from 2 to 500 and preferably from 2 to 200,and m is an integer ranging from 1 to 1 000, preferably from 1 to 700and better still from 6 to 200.

According to the invention, 80% of the groups R¹, R², R³ and R⁴ of thepolymer are preferably chosen from methyl, ethyl, phenyl and3,3,3-trifluoropropyl groups.

According to the invention, Y can represent various divalent groups,furthermore optionally comprising one or two free valencies to establishbonds with other moieties of the polymer or copolymer. Preferably, Yrepresents a group chosen from:

a) linear C₁ to C₂₀ and preferably C₁ to C₁₀ alkylene groups,

b) C₃₀ to C₅₆ branched alkylene groups possibly comprising rings andunconjugated unsaturations,

c) C₅-C₆ cycloalkylene groups,

d) phenylene groups optionally substituted with one or more C₁ to C₄₀alkyl groups,

e) C₁ to C₂₀ alkylene groups comprising from 1 to 5 amide groups,

f) C₁ to C₂₀ alkylene groups comprising one or more substituents chosenfrom hydroxyl, C₃ to C₈ cycloalkane, C₁ to C₃ hydroxyalkyl and C₁ to C₆alkylamine groups,

g) polyorganosiloxane chains of formula:

in which R¹, R², R³, R⁴, T and m are as defined above, and

h) polyorganosiloxane chains of formula:

The polyorganosiloxanes of the second family may be polymers comprisingat least one moiety corresponding to formula (II):

in which

R¹ and R³, which may be identical or different, are as defined above forformula (I),

R⁷ represents a group as defined above for R¹ and R³, or represents thegroup of formula —X-G—R⁹ in which X and G are as defined above forformula (I) and R⁹ represents a hydrogen atom or a linear, branched orcyclic, saturated or unsaturated, C₁ to C₅₀ hydrocarbon-based groupoptionally comprising in its chain one or more atoms chosen from O, Sand N, optionally substituted with one or more fluorine atoms and/or oneor more hydroxyl groups, or a phenyl group optionally substituted withone or more C₁ to C₄ alkyl groups,

R⁸ represents the group of formula —X-G—R⁹ in which X, G and R⁹ are asdefined above,

m₁ is an integer ranging from 1 to 998, and

m₂ is an integer ranging from 2 to 500.

According to the invention, the polymer used as gelling agent may be ahomopolymer, that is to say a polymer comprising several identicalmoieties, in particular moieties of formula (I) or of formula (II).

According to the invention, it is also possible to use a polymerconsisting of a copolymer comprising several different moieties offormula (I), that is to say a polymer in which at least one of thegroups R¹, R², R³, R⁴, X, G, Y, m and n is different in one of themoieties. The copolymer may also be formed from several moieties offormula (II), in which at least one of the groups R¹, R³, R⁷, R⁸, m₁ andm₂ is different in at least one of the moieties.

It is also possible to use a copolymer comprising at least one moiety offormula (I) and at least one moiety of formula (II), the moieties offormula (I) and the moieties of formula (II) possibly being identical toor different from each other.

According to one variant of the invention, it is also possible to use acopolymer furthermore comprising at least one hydrocarbon-based moietycomprising two groups capable of establishing hydrogen interactions,chosen from ester, amide, sulphonamide, carbamate, thiocarbamate, urea,urethane, thiourea, oxamido, guanidino and biguanidino groups, andcombinations thereof.

These copolymers may be block copolymers or graft copolymers.

According to a first embodiment of the invention, the groups capable ofestablishing hydrogen interactions are amide groups of formulae —C(O)NH—and —HN—C(O)—.

In this case, the gelling agent may be a polymer comprising at least onemoiety of formula (III) or (IV):

in which R¹, R², R³, R⁴, X, Y, m and n are as defined above.

Such a moiety may be obtained:

either by a condensation reaction between a silicone containing α,ω-carboxylic acid ends and one or more diamines, according to thefollowing reaction scheme:

or by reaction of two molecules of α-unsaturated carboxylic acid with adiamine according to the following reaction scheme:CH₂═CH—X¹—COOH+H₂N—Y—NH₂

CH₂═CH—X¹—CO—NH—Y—NH—CO—X¹—CH═CH₂followed by the addition of a siloxane to the ethylenic unsaturations,according to the following scheme:

in which X¹—(CH₂)₂— corresponds to X defined above and Y, R¹, R², R³, R⁴and m are as defined above;

or by reaction of a silicone containing α, ω-NH₂ ends and a diacid offormula HOOC—Y—COOH according to the following reaction scheme:

In these polyamides of formula (III) or (IV), m is preferably in therange from 1 to 700, more preferably from 15 to 500 and better stillfrom 10 to 100, and n is in particular in the range from 1 to 500,preferably from 1 to 100 and better still from 4 to 25,

X is preferably a linear or branched alkylene chain containing from 1 to30 carbon atoms and in particular 1 to 20 carbon atoms, and

Y is preferably an alkylene chain that is linear or branched or thatpossibly comprises rings and/or unsaturations, containing from 1 to 40carbon atoms, in particular from 1 to 20 carbon atoms and better stillfrom 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y canoptionally contain in its alkylene portion at least one of the followingelements:

1) 1 to 5 amide, urea, urethane or carbamate groups,

2) a C₅ or C₆ cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical ordifferent C₁ to C₃ alkyl groups.

In formulae (III) and (IV), the alkylene groups may also be substitutedwith at least one element chosen from the group consisting of:

a hydroxyl group,

a C₃ to C₈ cycloalkyl group,

one to three C₁ to C₄₀ alkyl groups,

a phenyl group optionally substituted with one to three C₁ to C₃ alkylgroups,

a C₁ to C₃ hydroxyalkyl group, and

a C₁ to C₆ aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:

in which R⁵ represents a polyorganosiloxane chain and T represents agroup of formula:

in which a, b and c are, independently, integers ranging from 1 to 10,and R¹⁰ is a hydrogen atom or a group such as those defined for R¹, R²,R³ and R⁴.

In formulae (III) and (IV), R¹, R², R³ and R⁴ preferably represent,independently, a linear or branched C₁ to C₄₀ alkyl group, preferably aCH₃, C₂H₅, n-C₃H₇ or isopropyl group, a polyorganosiloxane chain or aphenyl group optionally substituted with one to three methyl or ethylgroups.

As has been seen previously, the polymer may comprise identical ordifferent moieties of formula (III) or (IV).

Thus, the polymer may be a polyamide containing several moieties offormula (III) or (IV) of different lengths, i.e. a polyamidecorresponding to the formula:

in which X, Y, n and R¹ to R⁴ have the meanings given above, m₁ and m₂,which are different, are chosen in the range from 1 to 1 000, and p isan integer ranging from 2 to 300.

In this formula, the moieties may be structured to form either a blockcopolymer, or a random copolymer or an alternating copolymer. In thiscopolymer, the moieties may be not only of different lengths, but alsoof different chemical structures, for example containing differentgroups Y. In this case, the copolymer may correspond to the formula:

in which R¹ to R⁴, X, Y, m₁, m₂, n and p have the meanings given aboveand Y¹ is different from Y but chosen from the groups defined for Y. Aspreviously, the various moieties may be structured to form either ablock copolymer, or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the structuring agent mayalso consist of a graft copolymer. Thus, the polyamide containingsilicone units may be grafted and optionally crosslinked with siliconechains containing amide groups. Such polymers may be synthesized withtrifunctional amines.

In this case, the copolymer may comprise at least one moiety of formula:

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹¹ to R¹⁸ are groups chosen from the samegroup as R¹ to R⁴, m₁ and m₂ are numbers in the range from 1 to 1 000,and p is an integer ranging from 2 to 500.

In formula (VII), it is preferred that:

p is in the range from 1 to 25 and better still from 1 to 7,

R¹¹ to R¹⁸ are methyl groups,

T corresponds to one of the following formulae:

in which R¹⁹ is a hydrogen atom or a group chosen from the groupsdefined for R¹ to R⁴, and R²⁰, R²¹ and R²² are, independently, linear orbranched alkylene groups, and more preferably corresponds to theformula:

in particular with R²⁰, R²¹ and R²² representing —CH₂—CH₂—,

m₁ and m₂ are in the range from 15 to 500 and better still from 15 to45,

X¹ and X² represent —(CH₂)₁₀—, and

Y represents —CH₂—.

These polyamides containing a grafted silicone moiety of formula (VII)may be copolymerized with polyamide-silicones of formula (II) to formblock copolymers, alternating copolymers or random copolymers. Theweight percentage of grafted silicone moieties (VII) in the copolymermay range from 0.5% to 30% by weight.

According to the invention, as has been seen previously, the siloxaneunits may be in the main chain or backbone of the polymer, but they mayalso be present in grafted or pendent chains. In the main chain, thesiloxane units may be in the form of segments as described above. In thependent or grafted chains, the siloxane units may appear individually orin segments.

According to the invention, the preferred siloxane-based polyamides are:

polyamides of formula (III) in which m is from 15 to 50;

polyamides of formula (III) where m is from 30 to 500;

mixtures of two or more polyamides in which at least one polyamide has avalue of m in the range from 15 to 50 and at least one polyamide has avalue of m in the range from 30 to 50;

polymers of formula (V) with m₁ chosen in the range from 15 to 50 and m₂chosen in the range from 30 to 500 with the portion corresponding to m₁representing 1% to 99% by weight of the total weight of the polyamideand the portion corresponding to m₂ representing 1% to 99% by weight ofthe total weight of the polyamide;

mixtures of polyamide of formula (III) combining

1) 80% to 99% by weight of a polyamide in which n is equal to 2 to 10and in particular 3 to 6, and

2) 1% to 20% of a polyamide in which n is in the range from 30 to 500and in particular from 30 to 100;

mixtures of polyamide of formula (III) combining

1) 1% to 20% by weight of a polyamide where n is equal to 2 to 10, inparticular 3 to 6, and

2) 80% to 99% of a polyamide where n is in the range from 30 to 500, inparticular from 30 to 100;

polyamides corresponding to formula (VI) in which at least one of thegroups Y and Y¹ contains at least one hydroxyl substituent;

polyamides of formula (III) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polyamides of formula (III) in which X represents —(CH₂)₃— or —(CH₂)₁₀;and

polyamides of formula (III) in which the polyamides end with amonofunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

According to the invention, the ends of the polymer chains may end with:

a C₁ to C₅₀ alkyl ester group by introducing a C₁ to C₅₀ monoalcoholduring the synthesis,

a C₁ to C₅₀ alkylamide group by taking as stopping group a monoacid ifthe silicone is α, ω-diaminated, or a monoamine if the silicone is an α,ω-dicarboxylic acid.

According to one embodiment variant of the invention, it is possible touse a copolymer of silicone polyamide and of hydrocarbon-basedpolyamide, i.e. a copolymer comprising moieties of formula (III) or (IV)and hydrocarbon-based polyamide moieties. In this case, thepolyamide-silicone moieties may be arranged at the ends of thehydrocarbon-based polyamide.

Polyamide-based structuring agents containing silicones may be producedby silylic amidation of polyamides based on fatty acid dimer. Thisapproach involves the reaction of free acid sites existing on apolyamide as end sites, with oligosiloxane-monoamines and/oroligosiloxane-diamines (amidation reaction), or alternatively witholigosiloxane alcohols or oligosiloxane diols (esterification reaction).The esterification reaction requires the presence of acid catalysts, asis known in the art. It is desirable for the polyamide containing freeacid sites, used for the amidation or esterification reaction, to have arelatively high number of acid end groups (for example polyamides withhigh acid numbers, for example from 15 to 20).

For the amidation of the free acid sites of the hydrocarbon-basedpolyamides, siloxane diamines with 1 to 300, more particularly 2 to 50and better still 2, 6, 9.5, 12, 13.5, 23 or 31 siloxane groups, may beused for the reaction with hydrocarbon-based polyamides based on fattyacid dimers. Siloxane diamines containing 13.5 siloxane groups arepreferred, and, the best results are obtained with the siloxane diaminecontaining 13.5 siloxane groups and polyamides containing high numbersof carboxylic acid end groups.

The reactions may be carried out in xylene to extract the water producedfrom the solution by azeotropic distillation, or at higher temperatures(about 180 to 200° C.) without solvent. Typically, the efficacy of theamidation and the reaction rates decrease when the siloxane diamine islonger, that is to say when the number of siloxane groups is higher.Free amine sites may be blocked after the initial amidation reaction ofthe diaminosiloxanes by reacting them either with a siloxane acid, orwith an organic acid such as benzoic acid.

For the esterification of the free acid sites on the polyamides, thismay be performed in boiling xylene with about 1% by weight, relative tothe total weight of the reagents, of para-toluenesulphonic acid ascatalyst.

These reactions carried out on the carboxylic acid end groups of thepolyamide lead to the incorporation of silicone moieties only at theends of the polymer chain.

It is also possible to prepare a copolymer of polyamide-silicone, usinga polyamide containing free amine groups, by amidation reaction with asiloxane containing an acid group.

It is also possible to prepare a structuring agent based on a copolymerbetween a hydrocarbon-based polyamide and a silicone polyamide, bytransamidation of a polyamide having, for example, an ethylenediamineconstituent, with an oligosiloxane-α, ω-diamine, at high temperature(for example 200 to 300° C.), to carry out a transamidation such thatthe ethylenediamine component of the original polyamide is replaced withthe oligosiloxane diamine.

The copolymer of hydrocarbon-based polyamide and of polyamide-siliconemay also be a graft copolymer comprising a hydrocarbon-based polyamidebackbone with pendent oligosiloxane groups.

This may be obtained, for example:

by hydrosilylation of unsaturated bonds in polyamides based on fattyacid dimers;

by silylation of the amide groups of a polyamide; or

by silylation of unsaturated polyamides by means of an oxidation, thatis to say by oxidizing the unsaturated groups into alcohols or diols, toform hydroxyl groups that are reacted with siloxane carboxylic acids orsiloxane alcohols. The olefinic sites of the unsaturated polyamides mayalso be epoxidized and the epoxy groups may then be reacted withsiloxane amines or siloxane alcohols.

According to a second embodiment of the invention, the structuring agentconsists of a homopolymer or a copolymer comprising urethane or ureagroups.

As previously, the polymer may comprise polyorganosiloxane moietiescontaining two or more urethane and/or urea groups, either in thebackbone of the polymer or on side chains or as pendent groups.

The polymers comprising at least two urethane and/or urea groups in thebackbone may be polymers comprising at least one moiety corresponding tothe following formula:

in which R¹, R², R³, R⁴, X, Y, m and n have the meanings given above forformula (I), and U represents —O— or —NH—, such that:

corresponds to a urethane or urea group.

In this formula (VIII), Y may be a linear or branched C₁ to C₄₀ alkylenegroup, optionally substituted with a C₁ to C₁₅ alkyl group or a C₅ toC₁₀ aryl group. Preferably, a —(CH₂)₆— group is used.

Y may also represent a C₅ to C₁₂ cycloaliphatic or aromatic group thatmay be substituted with a C₁ to C₁₅ alkyl group or a C₅ to C₁₀ arylgroup, for example a radical chosen from the methylene-4,4-biscyclohexylradical, the radical derived from isophorone diisocyanate, 2,4- and2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4′-biphenylenemethane.Generally, it is preferred for Y to represent a linear or branched C₁ toC₄₀ alkylene radical or a C₄ to C₁₂ cycloalkylene radical.

Y may also represent a polyurethane or polyurea block corresponding tothe condensation of several diisocyanate molecules with one or moremolecules of coupling agents of the diol or diamine type. In this case,Y comprises several urethane or urea groups in the alkylene chain.

It may correspond to the formula:

in which B¹ is a group chosen from the groups given above for Y, U is—O— or —NH— and B² is chosen from:

linear or branched C₁ to C₄₀ alkylene groups,

C₅ to C₁₂ cycloalkylene groups, optionally-bearing alkyl substituents,for example one to three methyl or ethyl groups, or alkylenesubstituents, for example the diol radical: cyclohexanedimethanol,

phenylene groups that may optionally bear C₁ to C₃ alkyl substituents,and

groups of formula:

in which T is a hydrocarbon-based trivalent radical possibly containingone or more heteroatoms such as oxygen, sulphur and nitrogen and R⁵ is apolyorganosiloxane chain or a linear or branched C₁ to C₅₀ alkyl chain.

T can represent, for example:

with w being an integer ranging from 1 to 10 and R⁵ being apolyorganosiloxane chain.

When Y is a linear or branched C₁ to C₄₀ alkylene group, the —(CH₂)₂—and —(CH₂)₆— groups are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to5, preferably from 0 to 3 and more preferably equal to 1 or 2.

Preferably, B² is a linear or branched C₁ to C₄₀ alkylene group, inparticular —(CH₂)₂— or —(CH₂)₆— or the group:

with R⁵ being a polyorganosiloxane chain.

As previously, the polymer constituting the structuring agent may beformed from silicone urethane and/or silicone urea moieties of differentlength and/or constitution, and may be in the form of block or randomcopolymers.

According to the invention, the silicone may also comprise urethaneand/or urea groups no longer in the backbone but as side branches.

In this case, the polymer may comprise at least one moiety of formula:

in which R¹, R², R³, m₁ and m₂ have the meanings given above for formula(I),

U represents O or NH,

R represents a C₁ to C₄₀ alkylene group, optionally comprising one ormore heteroatoms chosen from O and N, or a phenylene group, and

R²⁴ is chosen from linear, branched or cyclic, saturated or unsaturatedC₁ to C₅₀ alkyl groups, and phenyl groups optionally substituted withone to three C₁ to C₃ alkyl groups.

The polymers comprising at least one moiety of formula (X) containsiloxane units and urea or urethane groups, and they may be used asstructuring agents in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group perbranch or may have branches containing two urea or urethane groups, oralternatively they may contain a mixture of branches containing one ureaor urethane group and branches containing two urea or urethane groups.

They may be obtained from branched polysiloxanes, comprising one or twoamino groups per branch, by reacting these polysiloxanes withmonoisocyanates.

As examples of starting polymers of this type containing amino anddiamino branches, mention may be made of the polymers corresponding tothe following formulae:

In these formulae, the symbol “/” indicates that the segments may be ofdifferent lengths and in a random order, and R represents a linearaliphatic group preferably containing 1 to 6 carbon atoms and betterstill 1 to 3 carbon atoms.

Such polymers containing branching may be formed by reacting a siloxanepolymer, containing at least three amino groups per polymer molecule,with a compound containing only one monofunctional group (for example anacid, an isocyanate or an isothiocyanate) to react this monofunctionalgroup with one of the amino groups and to form the groups capable ofestablishing hydrogen interactions. The amino groups may be on sidechains extending from the main chain of the siloxane polymer, such thatthe groups capable of establishing hydrogen interactions are formed onthese side chains, or alternatively the amino groups may be at the endsof the main chain, such that the groups capable of hydrogen interactionwill be end groups of the polymer.

As a procedure for forming a polymer containing siloxane moieties andgroups capable of establishing hydrogen interactions, mention may bemade of the reaction of a siloxane diamine and of a diisocyanate in asilicone solvent so as to provide a gel directly. The reaction may beperformed in a silicone fluid, the resulting product being dissolved inthe silicone fluid, at high temperature, the temperature of the systemthen being reduced to form the gel.

The polymers that are preferred for incorporation into the compositionsaccording to the present invention are siloxane-urea copolymers that arelinear and that contain urea groups as groups capable of establishinghydrogen interactions in the backbone of the polymer.

As an illustration of a polysiloxane ending with four urea groups,mention may be made of the polymer of formula:

in which Ph is a phenyl group and n is a number from 0 to 300, inparticular from 0 to 100, for example 50.

This polymer is obtained by reacting the following polysiloxanecontaining amino groups:

with phenyl isocyanate.

The polymers of formula (VIII) comprising urea or urethane groups in thechain of the silicone polymer may be obtained by reaction between asilicone containing α, ω-NH₂ or —OH end groups, of formula:

in which m, R¹, R², R³, R⁴ and X are as defined for formula (I), and adiisocyanate OCN—Y—NCO in which Y has the meaning given in formula (I);and optionally a diol or diamine coupling agent of formula H₂N—B²—NH₂ orHO—B²—OH, in which B² is as defined in formula (IX).

According to the stoichiometric proportions between the two reagents,diisocyanate and coupling agent, Y may have the formula (IX) with dequal to 0 or d equal to 1 to 5.

As in the case of the polyamide silicones of formula (II) or (III), itis possible to use in the invention polyurethane or polyurea siliconescontaining moieties of different length and structure, in particularmoieties whose lengths differ by the number of silicone moieties. Inthis case, the copolymer may correspond, for example, to the formula:

in which R¹, R², R³, R⁴, X, Y and U are as defined for formula (VIII)and m₁, m₂, n and p are as defined for formula (V).

Branched polyurethane or polyurea silicones may also be obtained using,instead of the diisocyanate OCN—Y—NCO, a triisocyanate of formula:

A polyurethane or polyurea silicone containing branches comprising anorganosiloxane chain with groups capable of establishing hydrogeninteractions is thus obtained. Such a polymer comprises, for example, amoiety corresponding to the formula:

in which X¹ and X², which are identical or different, have the meaninggiven for X in formula (I), n is as defined in formula (I), Y and T areas defined in formula (I), R¹¹ to R¹⁸ are groups chosen from the samegroup as R¹ to R⁴, m₁ and m₂ are numbers in the range from 1 to 1 000,and p is an integer ranging from 2 to 500.

As in the case of the polyamides, this copolymer can also comprisepolyurethane silicone moieties without branching.

In this second embodiment of the invention, the siloxane-based polyureasand polyurethanes that are preferred are:

polymers of formula (VIII) in which m is from 15 to 50;

polymers of formula (VIII) in which m is from 30 to 500;

mixtures of two or more polymers in which at least one polymer has avalue of m in the range from 15 to 50 and at least one polymer has avalue of m in the range from 30 to 50;

polymers of formula (XII) with m₁ chosen in the range from 15 to 50 andm₂ chosen in the range from 30 to 500 with the portion corresponding tom₁ representing 1% to 99% by weight of the total weight of the polymerand the portion corresponding to m₂ representing 1% to 99% by weight ofthe total weight of the polymer;

mixtures of polymer of formula (VIII) combining

1) 1% to 20% by weight of a polymer where n is equal to 2 to 10, inparticular 3 to 6, and

2) 80% to 99% of a polymer where n is in the range from 30 to 500, inparticular from 30 to 100,

copolymers comprising two moieties of formula (VIII) in which at leastone of the groups Y contains at least one hydroxyl substituent;

polymers of formula (VIII) synthesized with at least one portion of anactivated diacid (diacid chloride, dianhydride or diester) instead ofthe diacid;

polymers of formula (VIII) in which X represents —(CH₂)₃— or —(CH₂)₁₀—;and

polymers of formula (VIII) in which the polymers end with amonofunctional chain chosen from the group consisting of monofunctionalamines, monofunctional acids, monofunctional alcohols, including fattyacids, fatty alcohols and fatty amines, such as, for example,octylamine, octanol, stearic acid and stearyl alcohol.

As in the case of the polyamides, copolymers of polyurethane or polyureasilicone and of hydrocarbon-based polyurethane or polyurea may be usedin the invention by performing the reaction for synthesizing the polymerin the presence of an α, ω-difunctional block of non-silicone nature,for example a polyester, a polyether or a polyolefin.

As has been seen previously, gelling agents consisting of homopolymersor copolymers of the invention may contain siloxane moieties in the mainchain of the polymer and groups capable of establishing hydrogeninteractions, either in the main chain of the polymer or at the endsthereof, or on side chains or branches of the main chain. This maycorrespond to the following five arrangements:

in which the continuous line is the main chain of the siloxane polymerand the squares represent the groups capable of establishing hydrogeninteractions.

In case (1), the groups capable of establishing hydrogen interactionsare arranged at the ends of the main chain. In case (2), two groupscapable of establishing hydrogen interactions are arranged at each ofthe ends of the main chain.

In case (3), the groups capable of establishing hydrogen interactionsare arranged within the main chain in repeating moieties.

In cases (4) and (5), these are copolymers in which the groups capableof establishing hydrogen interactions are arranged on branches of themain chain of a first series of moieties that are copolymerized withmoieties not comprising groups capable of establishing hydrogeninteractions. The values n, x and y are such that the polymer has thedesired properties in terms of an agent for gelling fatty phases basedon silicone oil.

According to the invention, the structuring of the liquid fatty phasecontaining at least one silicone oil, is obtained with the aid of one ormore of the polymers mentioned above, in combination with one or morecompounds capable of reducing the melting temperature and the enthalpyof fusion of this or these polymers.

As examples of polymers that may be used, mention may be made of thesilicone polyamides obtained in accordance with Examples 1 to 3 ofdocument U.S. Pat. No. 5,981,680.

The polymers and copolymers used in the composition of the inventionadvantageously have a softening point from 65° C. to 190° C. Preferably,they have a softening point ranging from 70 to 130° C. and better stillfrom 80° C. to 105° C. This softening point is lower than that of theknown structuring polymers, which facilitates the use of the polymers,allows the use of volatile oils and limits the deteriorations of theliquid fatty phase.

They have good solubility in silicone oils and produce macroscopicallyhomogeneous compositions. Preferably, they have an average molecularmass from 500 to 200 000, for example from 1 000 to 100 000, preferablyfrom 2 000 to 200 000.

Compound Capable of Reducing the Enthalpy of Fusion and Possibly theMelting Temperature of the Structuring Polymer

The compound according to the invention contains one or more compoundscapable of lowering, reducing or decreasing the enthalpy of fusion (ΔH)and possibly the melting temperature (m.p.) of the structuring polymer;preferably capable of lowering the enthalpy of fusion (ΔH) and themelting temperature (m.p.). This or these compounds make it possible tofacilitate the application of the compositions and to improve thedeposit obtained with these compositions, that is to say that thisdeposit is a larger mass than that obtained under the same conditionswith compositions not containing these compounds. The said compound(s)are capable of lowering, decreasing or reducing the enthalpy of fusionand possibly the melting temperature of the structuring polymer(s) ofthe fatty phase.

The expression lowering of the enthalpy of fusion is understood to meanthat the polymer, once it has been brought into contact with this orthese compounds, has an enthalpy, expressed relative to the mass of thepolymer present, less than that which it exhibits in the pure state.

The enthalpy of fusion is measured using differential scanningcalorimetry, for example the calorimeter sold under the name MDSC 2920by the company TA Inst., by the so-called power compensatingcalorimetric analysis technique (Differential Scanning Calorimetry), inwhich a temperature rise of 2° C. per minute is applied.

The enthalpy of fusion corresponds to the surface under the curve of thethermogram obtained.

The thermogram is the power compensating differential calorimetricenthalpy curve: this curve represents the quantity of heat provided by aunit of time plotted on the y-axis, as a function of the temperature onthe x-axis.

The lowering of the enthalpy of fusion ΔH depends on the quantity ofcompound(s) above, in the composition. This quantity is such that it issufficient to cause a decrease in the enthalpy of fusion ΔH, thisdecrease is generally at least 3 J/g of pure polymer, preferably atleast 4 J/g of pure polymer, preferably still 5 to 10 J/g.

When the compound(s) are included in such quantities, all the effectsdescribed above are observed. In other words, the incorporation of thesecompounds, which are potentially capable of causing a decrease in theenthalpy of fusion, in a sufficient quantity, effectively allows them toexert this initially only potential effect.

In addition, the said compound(s) are generally also capable of loweringthe melting temperature (m.p.) of the structuring polymer.

The expression lowering of the melting temperature, of the meltingpoint, is understood to mean that the polymer, once it has been broughtinto contact with this or these compounds, has a melting temperatureless than that which it exhibits in the pure state.

The melting temperature, the melting point, correspond, according to theinvention, to the melting point which is measured using differentialscanning calorimetry, for example the calorimeter sold under the nameMDSC 2920 by the company TA Inst., by the so-called power compensatingcalorimetric analysis technique (Differential Scanning Calorimetry), inwhich a temperature rise of 2° C. per minute is applied. The meltingpoint considered is the point corresponding to the temperature of themost endothermic peak of the thermogram obtained. The thermogram wasdefined above.

To evaluate the lowering of the melting temperature caused by thecompounds capable of lowering the melting point included in thecomposition of the invention, the melting temperature of the purepolymer is first measured by the above method, and then the polymer issolubilized beyond its m.p. previously determined, with one or morecompounds capable of lowering or decreasing the melting temperature andthe melting point is measured by the same method, under the sameconditions, on the mixture of the polymer and of the compound(s).

The lowering of the melting temperature depends on the quantity ofcompound(s) above in the composition. This quantity should be such thatit is sufficient to cause a real decrease in, or lowering of the meltingtemperature of the polymer(s). This decrease or this lowering isgenerally at least 3° C., preferably at least 4° C., preferably stillfrom 5 to 20° C.

In addition, the compound(s) capable of lowering the melting temperatureand the enthalpy of fusion are advantageously compounds which lead tocompositions which are macroscopically homogeneous and/or which aresoluble or dispersible in the fatty phase of the composition.

A macroscopically homogeneous composition is a composition for which asingle phase is observed with the naked eye, at room temperature(between 20 and 25° C.).

The compound capable of lowering the enthalpy of fusion of thestructuring polymer is preferably soluble in the fatty phase of thecomposition, that is to say that the compound is in the form ofindividualized molecules distributed in the fatty phase.

The compound capable of lowering the enthalpy of fusion of thestructuring polymer is advantageously dispersible in the fatty phase ofthe composition, that is to say that the compound is in the form oflumps of molecules, having a size which is not detectable with the nakedeye, homogeneously distributed in the fatty phase.

These properties may be described by the fact that these compounds are“compatible” with the structuring polymer and optionally with the othercomponents of the composition.

Preferably, the compounds capable of lowering the enthalpy of fusion ofthe polymer also lower the melting temperature.

Preferably still, these compounds lower the melting temperature and leadto macroscopically homogeneous compositions.

In other words, preferably, the particular compounds used in thecomposition of the invention should simultaneously satisfy the threeconditions listed above and relating to the lowering of the meltingtemperature, to the lowering of the enthalpy of fusion and to theformation of macroscopically homogeneous compositions.

The compounds capable of causing a reduction in the enthalpy of fusionand optionally in the melting temperature of the structuring polymer is(are) chosen from hydrocarbon and/or silicone compounds comprising atleast one functional group comprising a free electron doublet capable ofinteracting with the hydrogen bonds of the polymer. This functionalgroup is chosen, for example, from hydroxyl (alcohol), carboxyl, amino,primary, secondary and tertiary amines, urea and urethane, ether andester.

The preferred functional group is the alcohol functional group and as aresult, the compounds capable of causing a decrease in the enthalpy offusion and optionally in the melting temperature of the structuringpolymer are preferably chosen from monoalcohols, polyols such as diolsand triols and the like, and polyol ethers.

In particular, the compound(s) capable of causing a decrease in theenthalpy of fusion and optionally in the melting temperature may bechosen from silicone diols.

Suitable silicone diols are described in particular in the document U.S.Pat. No. 5,969,172, to the description of which reference may be made,and are marketed by the company GENERAL ELECTRIC.

The compounds of this document correspond to the following formula:M_(a)M′_(b)D_(c)D′_(d)T_(e)T′_(f)Q_(g)

where the subscripts a, c, d, e, f and g are zero or a positive integer,provided that the sum of the subscripts b, d and f is one or higher;

where M has the formula:R₃ ^(I)Sio_(1/2)

where each R′ independently represents a monovalent hydrocarbon radicalhaving from 1 to 40 carbon atoms;

M′ has the formula:R_(3-h) ^(II)R_(h) ^(III)SiO_(1/2)

where each R^(II) is independently a monodivalent hydrocarbon radicalhaving from 1 to 40 carbon atoms, R^(III) is a monovalent hydrocarbonradical chosen from the group consisting of H₂(OH)CCH(OH)CH₂OCH₂CH₂CH₂—and (HOCH₂)₂C(CH₂CH₃)CH₂OCH₂CH₂CH₂— the subscript h is 1, 2 or 3;

D has the formula:R₂ ^(IV)SiO_(2/2)

where each R^(IV) is independently a monovalent hydrocarbon radicalhaving from 1 to 40 carbon atoms;

D′ has the formula:R_(2-i) ^(V)R_(i) ^(VI)SiO_(2/2)

where each R^(IV) is independently a monovalent hydrocarbon radicalhaving from 1 to 40 carbon atoms, R^(V) is a monovalent hydrocarbonradical chosen from the group consisting of H₂(OH)CCH(OH)CH₂OCH₂CH₂CH₂—and (HOCH₂)₂C(CH₂CH₃)CH₂OCH₂CH₂CH₂— and the subscript i is 1 or 2;

T has the formula:R^(VII)SiO_(3/2)

where each R^(VII) is independently a monovalent hydrocarbon radicalhaving from 1 to 40 carbon atoms,

T′ has the formula:R^(VIII)SiO_(3/2)

where R^(VIII) is a monovalent hydrocarbon radical chosen from thegroup-consisting of H₂ (OH)CCH(OH)CH₂OCH₂CH₂CH₂— and (HOCH₂)₂C(CH₂CH₃)CH₂OCH₂CH₂CH₂— and Q has the formula SiO_(4/2).

The preferred compounds are the compounds indicated in the followingTable 3:

TABLE 3 Compound Structure Functional group 1 MD₄′M 1,3-DIOL 2 M′ D₃M′1,3-DIOL 3 MD_(6,4)D′₅M 1,3-DIOL 4 MD₁₀D′₇M 1,3-DIOL 5 M′ D₃M′ 1,2-DIOL6 M′ D₅M′ 1,3-DIOL 7 MD_(6,4)D′₅M 1,2-DIOL 8 MD₃D′₃M 1,2-DIOL 9 MD₇D′₃M1,3-DIOL 10 M′ D₅M′ 1,2-DIOL 11 M′ D_(7,5)M′ 1,3-DIOL 12 MD₇D′₃M1,2-DIOL 13 M′ D_(7,5)M′ 1,2-DIOL 14 M′ D₁₀M′ 1,3-DIOL 15 M′ D₁₀M′1,2-DIOL 16 MD₂₀D′₃M 1,3-DIOL 17 M′ D₂₅M′ 1,2-DIOL

In Table 3: 1,3-DIOL means that the functional group, that is to sayR^(III), R^(V) or R^(VIII) is a group (HOCH₂)₂C(CH₂CH₃)CH₂OCH₂CH₂CH₂—namely a group derived from the monoallyl ether of trimethylolpropane(TMPMAE), and 1,2-DIOL means that the functional group is a groupH₂(OH)CCH(OH)CH₂OCH₂CH₂CH₂—, namely a group derived frommonoallylglycerine.

In Table 3, the compounds further preferred are M′D₃M′, M′D_(7,5)M′,M′D₁₀M′ and M′D₂₅M′.

The compounds capable of causing a decrease in the enthalpy of fusionand optionally in the melting temperature may also be chosen fromcompounds of the oxyalkylenated polydi(alkyl)siloxane type, in which thealkyl groups of the siloxane have from 1 to 4 carbon atoms and thealkylene group has from 1 to 4 carbon atoms, preferably the alkyl groupsof polydi(alkyl)siloxane are methyl groups and the oxyalkylene groupsare oxypropylene and/or oxyethylene groups and the compounds are PDMSoxypropylene and/or oxyethylene.

Compounds of this type are known by the name dimethicone polyol orcopolyol (PDMS-EO-PO) among which there may be mentionedpolydimethylsiloxane oxyethylene (7/9 EO) oxypropylene (10/14 PO) fromDEGUSSA, marketed under the reference ABIL B 8873, orpolydimethylsiloxane oxyethylene (200 E) oxypropylene (200 P) knownunder the INCI name PEG/PPG-17/18 dimethicone and marketed by DOWCORNING under the name “Q2-5220 RESIN modifier”.

Other compounds capable of causing a decrease in the enthalpy of fusionand optionally the melting temperature of the polymer are monoalkylethers of polyalkylene (1-4 carbon atoms) glycols, for example monoalkylethers of polypropylene glycol or of polyalkylene glycol, such as themonomyristyl ether of polypropylene glycol of formula:H—[OCH(CH₃)CH₂]_(n)O—(CH₂)₁₃—CH₃

with n=2 to 200.

Another family of compounds capable of causing a decrease in theenthalpy of fusion and possibly the melting temperature of thestructuring polymer are the linear or branched aliphatic monoalcoholshaving more than 8 carbon atoms, for example from 12 to 26 carbon atomssuch as 2-butyloctanol, 2-hexyldecanol, 2-undecyldecanol,2-undecylpentadecanol, oleyl alcohol, a preferred alcohol beingoctyldodecanol.

It is possible to include a single compound capable of reducing theenthalpy of fusion and possibly the melting temperature of the polymeror of the polymers or alternatively several of these compounds which mayeach be chosen from any of the groups and families of compounds definedabove.

The content of compound or of compound(s) capable of lowering theenthalpy of fusion and possibly the melting temperature of thepolymer(s) is generally from 5 to 25% by weight, preferably from 10 to20% by weight.

This quantity is the sufficient quantity defined above and which makesit possible to obtain a decrease in the enthalpy of fusion of thepolymer and possibly in the melting temperature of the polymer generallyof at least 3 J/g and of at least 3° C. respectively.

The use of compounds reducing the enthalpy of fusion and possibly themelting temperature of the polymers, such as PASi's, in cosmeticcompositions is not known in the art. The combination of such compoundswith the particular polymers according to the invention is neitherdescribed nor suggested in the prior art. Nothing made it possible tothink, in the light of the prior art, that such a combination could leadto a surprising improvement in the properties, in particular in the easeof application and possibly the gloss of a cosmetic compositioncomprising this combination, as well as an improvement in theproperties, in particular in the mass and possibly the gloss of adeposit obtained from a cosmetic composition comprising thiscombination.

The quantities of the compound(s) lowering the enthalpy of fusion andpossibly the melting temperature of the polymer(s), and the structuringpolymer(s) may be chosen according to the desired hardness and thedesired stability of the compositions and according to the specificapplication envisaged. The respective quantities of the (at least one)structuring polymer and of the compound(s) lowering the enthalpy offusion and possibly the melting point may be such that a disintegratablesolid which does not run under the effect of its own weight is obtained.

According to one of the embodiments of the invention, which correspondsto a stick, the composition preferably has a hardness ranging from 20 to2 000 gf and better still from 20 to 900 gf, particularly from 20 to 600gf, and for example from 150 to 450 gf. This hardness may be measuredaccording to a method of penetration of a probe into the saidcomposition and in particular with the aid of a texture analyser (forexample TA-TXT2i from Rheo) equipped with an ebonite cylinder 25 mm inheight and 8 mm in diameter. The hardness measurement is carried out at20° C. at the centre of five samples of the said composition. Thecylinder is introduced into each sample of composition at a pre-speed of2 mm/s, then at a speed of 0.5 mm/s and finally at a post-speed of 2mm/s, the total displacement being 1 mm. The recorded hardness value isthat of the maximum peak. The measurement error is ±50 gf.

The hardness may also be measured by the “cheese wire” method, whichconsists in cutting a tube of lipstick 12.7 mm in diameter and inmeasuring the hardness at 20° C., using a DFGHS 2 tensile testingmachine from the company Indelco-Chatillon, travelling at a speed of 100mm/minute. It is expressed as the shear force (expressed in gram-force)required to cut a stick under these conditions. According to thismethod, the hardness of a composition in stick form according to theinvention ranges from 30 to 300 gf, preferably from 30 to 250 gf and forexample from 30 to 200 gf, even better from 30 to 120 gf, when thediameter of the stick is equal to 12.7 mm.

The hardness of the composition may moreover be lower as long as thecomposition is self-supporting and can disintegrate easily to form asatisfactory deposit on the skin and the lips. By virtue of the presencein the composition of the invention of a compound capable of loweringthe enthalpy of fusion and possibly the temperature of the polymer, aneasy application and a satisfactory deposit in sufficient quantities areobtained in all cases.

In addition, with these hardness values, the composition of theinvention shows good impact strength.

Generally, the silicone polymer/compound capable of lowering theenthalpy of fusion and possibly the melting temperature of the polymermass ratio is generally in the range from 0.1 to 50, preferably from 0.5to 25 and even better from 1 to 15.

The structuring silicone polymer preferably represents 5 to 30% byweight of the composition.

Other Additives

The composition of the invention may also comprise any ingredientusually used in the field under consideration, and especially thosechosen from fillers, dyes that are soluble in polyols or in the fattyphase, antioxidants, essential oils, preserving agents, perfumes,liposoluble polymers, especially hydrocarbon-based liposoluble polymerssuch as polyalkylenes or polyvinyl laurate, liquid-fatty-phasestructuring agents, waxes, gums, resins, surfactants, for instancetrioleyl phosphate, additional cosmetic or dermatological active agentssuch as, for example, water, emollients, moisturizers, vitamins, liquidlanolin, essential fatty acids, lipophilic sunscreens or sunscreens thatare soluble in polyols, and mixtures thereof. The composition accordingto the invention may also contain lipid vesicles of ionic and/ornon-ionic type. These ingredients, besides the water, may be present inthe composition in the usual manner in a proportion of from 0% to 20%,preferably from 0.01% to 20%, of the total weight of the composition andbetter still from 0.1% to 10%.

In the case where the composition contains an aqueous phase, which isthe case for a simple or multiple emulsion, this aqueous phase canrepresent 0.1% to 70% of the total weight of the composition, especiallyfrom 0.5% to 40% and better still from 1% to 20%. This aqueous phase cancontain any water-miscible compound such as polyols and may beoptionally gelled with a suitable gelling agent.

Needless to say, the person skilled in the art will take care to selectthe optional additional ingredients and/or the amount thereof such thatthe advantageous properties of the composition according to theinvention are not, or are not substantially, adversely affected by theenvisaged addition.

The compositions of the invention may in particular contain one or morewaxes, for example polyethylene wax, but the use of wax is avoided if itis desired to obtain glossy, or even transparent products. Generally,the amount of wax does not exceed 20% and preferably 10%; it represents,for example, from 3% to 5% of the total weight of the composition. Evenin the absence of waxes or in the presence of a small quantity of waxes,the compositions according to the invention all exhibit the advantageousproperties listed above.

The composition according to the invention may be in the form of anoptionally tinted care composition for keratinous materials such as theskin, the lips and/or the superficial body growths, in the form of a sunprotection or care composition, especially in the form of amake-up-removing product, in the form of a stick or a dome, or in castform. It can especially be used as a care base for the skin, thesuperficial body growths or the lips (lip balms, for protecting the lipsagainst the cold and/or sunlight and/or the wind, or a care cream forthe skin, the nails or the hair).

The composition of the invention may be provided in particular in theform of a soft, transparent gel, or of a transparent stick.

The composition of the invention may also be in the form of afoundation, optionally having care or treatment properties, a blusher, aface powder, an eyeshadow, a concealer product, an eyeliner or a make-upproduct for the body; a lip make-up, for instance a lipstick, a lipgloss or a pencil, optionally having care or treatment properties; amake-up for the superficial body growths, for instance the nails or theeyelashes, in particular in the form of a mascara cake, or for theeyebrows and the hair, especially in the form of a pencil.

In particular, the composition of the invention may be a cosmeticproduct containing cosmetic active agents, for instance essential oils,vitamins, moisturizers, sunscreens and ceramides.

In the case of make-up compositions, hydrophobic or hydrophilic solidparticles may constitute the pigment(s) for making up the skin, the lipsand/or the superficial body growths.

Needless to say, the composition of the invention must be cosmeticallyor dermatologically acceptable, that is to say that it must contain anon-toxic physiologically acceptable medium that can be applied to theskin, the superficial body growths or the lips of human beings. For thepurposes of the invention, the expression “cosmetically acceptable”means a composition of pleasant appearance, odour and feel.

Moreover, the make-up or care compositions in accordance with theinvention must comprise at least 10% by mass of a non-volatile oil(silicone oil or non-silicone oil) and/or of a pasty or viscous productin order to obtain a product which is comfortable and which does notcause tightness.

The expression pasty product is understood to mean a viscous fattysubstance containing a liquid fraction and a solid fraction. For thepurposes of the invention, the expression “pasty fatty substances” meansfatty substances with a melting point ranging from 20 to 55° C. andpreferably 25 to 45° C., and/or a viscosity at 40° C. ranging from 0.1to 40 Pa·s (1 to 400 poises) and preferably 0.5 to 25 Pa·s measuredusing a Contraves TV or Rheomat 180 viscometer, equipped with a spindlerotating at 240 min⁻¹ for a power supply at 60 Hz or at 200 min⁻¹ for apower supply at 50 Hz or alternatively measured in the newtonian domainof a flow observed on a Haake Rs75 rheometer in a flat cone spindle at40° C.

A person skilled in the art can select the spindle for measuring theviscosity, on the basis of his general knowledge, so as to be able tomeasure the viscosity of the tested pasty compound.

The melting point values correspond, according to the invention and asalready indicated above, to the most endothermic melting peak measuredby the “Differential Scanning Calorimetry” method with a temperaturerise of 20° C./min.

By way of example of pasty products that may be used in the invention,mention may be made of lanolins and lanolin derivatives, for instanceacetylated lanolins or oxypropylenated lanolins or isopropyl lanolate,with a viscosity of 18 to 21 Pa·s and preferably 19 to 20.5 Pa·s, and/ora melting point of 30 to 55° C., preferably 30 to 40° C., and mixturesthereof. Esters of fatty acids or of fatty alcohols may also be used,especially those containing 20 to 65 carbon atoms (melting point ofabout 20 to 35° C. and/or viscosity at 40° C. ranging from 0.1 to 40Pa·s), for instance triisostearyl citrate or cetyl citrate; arachidylpropionate; polyvinyl laurate; cholesterol esters, for instancetriglycerides of plant origin such as hydrogenated plant oils, viscouspolyesters, for instance poly(12-hydroxystearic acid) and mixturesthereof. Triglycerides of plant origin that may be used includehydrogenated castor oil derivatives, such as “THIXINR” from Rheox.

Mention may also be made of silicone-based pasty fatty substances suchas polydimethylsiloxanes (PDMSs) containing pendent chains of the alkylor alkoxy type containing from 8 to 24 carbon atoms, and having amelting point of 20-55° C., for example 20 to 40° C., for instancestearyl dimethicones, especially those sold by the company Dow Corningunder the trade names DC2503 and DC25514, and mixtures thereof.

The pasty fatty substance(s) may be present in a proportion of from 0 to60% by weight relative to the total weight of the composition,preferably in a proportion of 0.1-45% by weight and even more preferablyin a proportion of 2-30% by weight.

According to the invention, the composition generally comprises, inaddition, solid particles chosen from fillers and pigments (includingpearlescent pigments) and mixtures thereof.

The expression pigments is understood to mean any solid particleinsoluble in the composition which serves to give and/or modify a colourand/or an iridescent appearance.

The pigments may be white or coloured, inorganic and/or organic, coatedor not. The inorganic pigments may be chosen for example from zincoxides, iron oxides, titanium oxides and mixtures thereof. There maythus be mentioned, among the inorganic pigments, titanium or zincdioxide, optionally surface-treated, zirconium or cerium oxides, andiron or chromium oxides, manganese violet, ultramarine blue, chromiumhydrate and ferric blue. Among the organic pigments, there may bementioned carbon black, pigments of the D & C type, and lacquers basedon carmine, barium, strontium, calcium or aluminium. The pigments mayrepresent from 0.1 to 50%, preferably from 0.5 to 40%, and even betterfrom 2 to 30% of the total weight of the composition.

According to the invention, the composition may furthermore containcolouring matter which may be chosen from lipophilic dyes, hydrophilicdyes, and mixtures thereof.

This colouring matter is generally present in an amount of 0.01 to 50%of the total weight of the composition; preferably 5 to 30%, if it ispresent. It should be noted that a colouring effect may also be providedby the pigments (and pearlescent pigments) already described above inthe context of solid particles.

The liposoluble dyes are, for example, Sudan red, DC Red 17, DC Green 6,β-carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DCOrange 5, quinoline yellow and annatto.

The hydrophilic dyes are in particular beet juice and methylene blue.Soluble dyes can represent from 0% to 20% of the weight of thecomposition and better still from 0.1% to 6% (if present).

The composition according to the invention may be manufactured by knownmethods, generally used in the cosmetic or dermatological field. It maybe manufactured by the method which consists in heating, the polymer atleast to its softening point, adding thereto the optional waxes and/orpasty compounds, the oil(s), the compound(s) lower the enthalpy offusion and possibly the melting temperature of the polymer, and then inmixing the whole until a clear solution is obtained. The colouringmatter and/or the solid particles and the additives are then added, withstirring. The homogeneous mixture obtained can then be cast in asuitable mould such as a lipstick mould, or directly into the packagingarticles, especially a case or dish.

The subject of the invention is also a make-up structured solidcomposition for the skin, the lips and/or the superficial body growths,containing at least one pigment in a sufficient quantity for applyingmake-up to the skin, the lips and/or the superficial body growths and aliquid continuous fatty phase structured with at least one polymer(homopolymer or copolymer) having a weight-average molecular massranging from 500 to 500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the said-liquid fatty phase comprising at least one compound capable oflowering the enthalpy of fusion and possibly the melting temperature ofthe structuring polymer,

the said composition being optionally provided in the form of a solid,and the pigment, the liquid fatty phase, the compound capable oflowering the enthalpy of fusion and possibly the melting temperature ofthe structuring polymer and the structuring polymer forming aphysiologically acceptable medium.

This make-up composition is preferably self-supporting.

The subject of the invention is also a lipstick structured composition,containing at least one pigment in a sufficient quantity for applyingmake-up to the lips and a liquid continuous fatty phase structured withat least one polymer (homopolymer or copolymer) having a weight-averagemolecular mass ranging from 500 to 500 000, containing at least onemoiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase comprising at least one compound capable oflowering the enthalpy of fusion and possibly the melting temperature ofthe structuring polymer, and the pigment, the fatty phase, the polymer,and the compound capable of lowering the enthalpy of fusion and possiblythe melting temperature of the structuring polymer forming aphysiologically acceptable medium.

The invention relates to a cosmetic care, make-up or treatment methodfor the keratinous materials of human beings, comprising the applicationto the keratinous materials of a cosmetic composition in accordance withthe invention.

The subject of the invention is also the use, in a cosmetic compositionor for the manufacture of a physiologically acceptable composition,containing a continuous liquid fatty phase, of a sufficient quantity ofat least one polymer (homopolymer or copolymer) having a weight-averagemolecular mass ranging from 500 to 500 000, containing at least onemoiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase optionally consisting partially or totally ofsilicone oil(s) having a flash point equal to or greater than 40° C. andcomprising one compound at least capable of lowering the enthalpy offusion and possibly the melting temperature of the structuring polymer,

the said composition being provided in the form of a self-supportingsolid with a hardness ranging from 20 to 2 000 gf and preferably from 20to 900 gf and even better from 20 to 600 gf.

The subject of invention is also the use of a continuous liquid fattyphase essentially structured with a sufficient quantity of at least onepolymer (homopolymer or copolymer) having a weight-average molecularmass ranging from 500 to 500 000, containing at least one moietycomprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase optionally consisting partially or totally ofvolatile oil(s) having a flash point equal to or greater than 40° C. andcomprising at least one compound capable of lowering the enthalpy offusion and possibly the melting temperature of the polymer, in acosmetic composition or for the manufacture of a physiologicallyacceptable composition which is easy to apply and/or gives a depositwith a large mass.

The subject of the invention is also the use of a sufficient quantity ofat least one polymer (homopolymer or copolymer) having a weight-averagemolecular mass ranging from 500 to 500 000, containing at least onemoiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

in a cosmetic composition or for the manufacture of a physiologicallyacceptable composition, containing a liquid continuous fatty phase andat least one compound capable of lowering the enthalpy of fusion andpossibly the melting temperature of the polymer, to structure the saidcomposition in the form of a self-supporting solid.

The subject of the invention is also the use of the combination of acontinuous liquid fatty phase essentially structured with a sufficientquantity of at least one polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in a chain of the moiety or in the form of        a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase optionally consisting partially or totally ofvolatile oil(s) having a flash point equal to or greater than 40° C. andcomprising at least one compound capable of lowering the enthalpy offusion and possibly the melting temperature of the polymer, in acosmetic composition or for the manufacture of a physiologicallyacceptable composition, as agent for facilitating the application of thesaid composition, and/or optionally increasing its gloss and the glossof a deposit of the said composition.

The invention additionally relates to the use of a continuous liquidfatty phase, optionally structured with a sufficient quantity of atleast one structuring polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group consisting of 1 to 1000        organosiloxane units in a chain of the moiety or in the form of        a graft, and    -   at least two groups capable of establishing hydrogen        interactions, chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

the liquid fatty phase optionally partially or totally consisting ofvolatile oil(s) and comprising at least one compound capable of loweringthe enthalpy of fusion and possibly the melting temperature of thepolymer, in a cosmetic composition or for the manufacture of aphysiologically acceptable composition as an agent for increasing themass of a deposit of the said composition.

According to an advantageous characteristic of these uses, thecomposition has a hardness of 20 to 2 000 gf, preferably of 20 to 900 gfand even better of 20 to 600 gf.

The invention also relates to a cosmetic method for facilitating theapplication of a cosmetic composition containing a liquid fatty phase,consisting in structuring the said fatty phase with a sufficientquantity of at least one polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group, consisting of 1 to 1 000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        biguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

and in adding at least one compound capable of lowering the enthalpy offusion and possibly the melting temperature of the polymer to thecomposition.

The invention also relates to a cosmetic method for increasing the massof a deposit of a cosmetic composition containing a liquid fatty phaseconsisting in structuring the said fatty phase with a sufficientquantity of at least one polymer (homopolymer or copolymer) having aweight-average molecular mass ranging from 500 to 500 000, containing atleast one moiety comprising:

-   -   at least one polyorganosiloxane group consisting of 1 to 1000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions, chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        bioguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

and in adding at least one compound capable of decreasing the enthalpyof fusion and possibly the melting temperature of the polymer to thecomposition.

The invention finally relates to the use, in a cosmetic composition or aphysiologically acceptable composition comprising a continuous liquidfatty phase structured with at least one polymer (homopolymer orcopolymer) having a weight-average molecular mass ranging from 500 to500 000, containing at least one moiety comprising:

-   -   at least one polyorganosiloxane group consisting of 1 to 1000        organosiloxane units in the chain of the moiety or in the form        of a graft, and    -   at least two groups capable of establishing hydrogen        interactions, chosen from ester, amide, sulphonamide, carbamate,        thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and        bioguanidino groups, and combinations thereof,

the polymer being solid at room temperature and soluble in the liquidfatty phase at a temperature of 25 to 250° C.,

of a sufficient quantity of a compound capable of lowering the enthalpyof fusion and possibly the melting temperature of the polymer so as tofacilitate the application of the said composition and increase the massof a deposit of the said composition.

DETAILED DISCLOSURE OF THE INVENTION

The invention is illustrated in greater detail in the following examplesof make-up formulation given by way of illustration and withoutlimitation. The quantities are given as % by mass. The chemicalcompounds are given mainly as the CTFA (“International CosmeticIngredient Dictionary”) name.

Example 1 (Comparative)

In this example not conforming to the invention, a makeup formula forthe lips and the face was prepared exclusively from silicones with, asstructuring agent, silicone polyamide and, as oil, a phenylatedsilicone.

The formula is then pigmented and cast in a pot.

The composition of the formula prepared is given below:

Compound % Silicone polyamide 25 of DP*45 obtained according to theteaching of patent US-5 981 680 Phenylated silicone 66.34 Pigments 8.66TOTAL 100 *DP: degree of polymerization.

The silicone polymer is melted at 110° C. and mixed with a portion ofthe oil in order to obtain a liquid mixture. The pigments are ground inparallel in the remainder of the oil. Finally, the pigmented groundproduct is mixed with the oil plus gelling agent mixture at 110° C.

The deposit obtained on the hand from the stick is fine andnonhomogeneous.

In conclusion, it appears that the formula prepared in this comparativeexample is hard and deposits only very little colour during theapplication which is difficult.

Example 2

In this example in accordance with the invention, a makeup formula isprepared whose composition is similar to that of claim 1, except that20% by mass of a compound according to the invention which lowers themelting temperature of the polymer, namely octadodecanol, is added tothe formula.

The composition of the formula prepared is given below:

Compound % Silicone polyamide 25 of DP*45 obtained according to theteaching of patent US-5 981 680 Octadodecanol 20 Phenylated silicone46.34 Pigments 8.66 TOTAL 100 *DP: degree of polymerization.

The silicone polymer is melted at 110° C. and mixed with part of thesilicone oil and with the octadodecanol in order to obtain a liquidmixture. The pigments are ground in parallel in the remainder of theoil. Finally, the pigmented ground product is mixed with the oil plusgelling agent mixture at 110° C.

The appearance at room temperature of the 12.7 mm stick obtained afterunmoulding is smooth, homogeneous and glossy.

The deposit obtained, prepared under the same conditions as in Example1, is larger than that of Example 1.

The deposit is glossy.

In conclusion, by virtue of the presence of octadodecanol, the formulaaccording to the invention is easier to apply and the deposit has a moreintense colour, which allows the making up of the lips, for example.Moreover, an improvement is noted in the gloss of the product and of thedeposit.

REFERENCES

[1] EP-A-1 068 856

[2] WO-A-01/97758

[3] U.S. Pat. No. 5,874,069

[4] U.S. Pat. No. 5,919,441

[5] U.S. Pat. No. 6,051,216

[6] WO-A-02/17870

[7] WO-A-02/17871

[8] EP-A-1 177 784

[9] U.S. Pat. No. 5,412,004

[10] EP-A-1 048, 686

[11] U.S. Pat. No. 5,981,680

[12] WO-A-99/06473

[13] U.S. Pat. No. 6,353,076

1. A make-up cosmetic composition comprising: at least one pigment and aliquid continuous fatty phase comprising at least one structuringpolymer and 5 to 25% by weight of the composition of at least onecompound capable of reducing the enthalpy of fusion of the at least onestructuring polymer which is a linear or a branched aliphaticmonoalcohol having more than 8 carbon atoms but not more than 26 carbonatoms; wherein the at least one structuring polymer has a weight-averagemolecular mass ranging from 500 to 500,000, is a solid at roomtemperature, and is soluble in the liquid fatty phase at a temperatureof 25 to 250° C.; and wherein the at least one structuring polymercomprises at least one moiety of formula (III) or (IV):

in which: 1) R¹, R², R³ and R⁴, which may be identical or different, areselected from the group consisting of an A-substituent, a B-substituent,and a C-substituent: wherein the A-substituent is a linear, branched orcyclic, saturated or unsaturated, C₁ to C₄₀ hydrocarbon, whichoptionally comprises in the chain of the hydrocarbon one or more of anoxygen atom, a sulphur atom, and a nitrogen atom, and optionally ispartially or totally fluorinated; wherein the B-substituent is a C₆ toC₁₀ aryl group, which is optionally substituted with one or more C₁ toC₄ alkyl groups, and wherein the C-substituent is at least onepolyorganosiloxane chain, which optionally comprises in the chain of thepolyorganosiloxane one or more of an oxygen atom, a sulfur atom, and anitrogen atom; 2) the groups X, which may be identical or different,represent a linear or branched C₁ to C₃₀ alkylenediyl group, whichoptionally comprises in the chain of the alkylenediyl group one or moreoxygen atom and/or nitrogen atom; 3) Y is a saturated or unsaturated, C₁to C₅₀ linear or branched divalent alkylene, arylene, cycloalkylene,alkylarylene or arylalkylene group, optionally comprising one or moreoxygen atom, sulfur atom, and/or nitrogen atom, and/or bearing assubstituent one of the following atoms or groups of atoms: fluorine,hydroxyl, C₃ to C₈ cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyloptionally substituted with 1 to 3 C₁ to C₃ alkyl groups, C₁ to C₃hydroxyalkyl and C₁ to C₆ aminoalkyl, or 4) Y represents a groupcorresponding to the formula:

wherein T represents a linear or branched, saturated or unsaturated, C₃to C₂₄ trivalent or tetravalent hydrocarbon group optionally substitutedwith a polyorganosiloxane chain, and optionally comprising one or moreatoms chosen from O, N and S, or T represents a trivalent atom chosenfrom N, P and Al, and R⁵ represents a linear or branched C₁ to C₅₀ alkylgroup or a polyorganosiloxane chain, optionally comprising one or moreester, amide, urethane, thiocarbamate, urea, thiourea and/orsulphonamide groups, which optionally is linked to another chain of thepolymer; and 5) n is an integer ranging from 2 to 500, and m is aninteger ranging from 1 to 1,000, wherein the at least one pigment, theliquid fatty phase, the at least one structuring polymer, and the atleast one compound capable of reducing the enthalpy of fusion of the atleast one structuring polymer form a physiologically acceptable medium.2. The composition according to claim 1, in which the liquid fatty phasefurther comprises at least one hydrocarbon oil.
 3. The compositionaccording to claim 1, wherein the liquid fatty phase further comprisesat least one silicone oil.
 4. The composition according to claim 3,wherein the liquid fatty phase comprises at least 30% by weight ofsilicone oil.
 5. The composition according to claim 1, wherein theliquid fatty phase further comprises at least one volatile oil having aflash point ranging from 35 to 135° C.
 6. The composition according toclaim 5, wherein the volatile oil is selected from the group consistingof isododecane, isohexadecane, C₈-C₁₆ isoparaffins, isohexylneopentanoate, isodecyl neopentanoate, and mixtures thereof.
 7. Thecomposition according to claim 5, wherein the volatile oil is selectedfrom the group consisting of: isododecane, octyltrimethicone,hexyltrimethicone, decamethylcyclopentasiloxane D5,octamethylcyclotetrasiloxane D4, dodecamethylcyclohexasiloxane D6,heptamethyloctyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane, a polydimethylsiloxane having a viscosity of1.5 cSt at 25° C., a polydimethyl-siloxane having a viscosity of 2 cStat 25° C., a polydimethylsiloxane having a viscosity of 3 cSt at 25° C.,a polydimethylsiloxane having a viscosity of 5 cSt at 25° C., andmixtures thereof.
 8. The composition according to claim 5, wherein thevolatile oil is selected from the group consisting ofperfluoropolyethers, perfluoroalkanes, perfluoroadamantames, esters ofperfluoroalkyl phosphates, fluorinated ester oils, and mixtures thereof.9. The composition according to claim 5, wherein the at least onevolatile oil ranges from 3 to 89.4% of the total weight of thecomposition.
 10. The composition according to claim 1, wherein, theliquid fatty phase further comprises at least one volatile oil having avapour pressure ranging from 0.01 to 300 mmHg, at 25° C.
 11. Thecomposition according to claim 1, wherein the liquid fatty phase furthercomprises a nonvolatile silicone oil.
 12. The composition according toclaim 1, wherein R¹, R², R³ and R⁴ represent, independently, a linear orbranched C₁ to C₄₀ alkyl group.
 13. The composition according to claim1, wherein the at least one structuring polymer ranges from 0.5 to 80%of the total weight of the composition.
 14. The composition according toclaim 13, wherein the at least one structuring polymer ranges from 5 to40% of the total weight of the composition.
 15. The compositionaccording to claim 1, wherein the liquid fatty phase ranges from 5 to99% of the total weight of the composition.
 16. The compositionaccording to claim 1, wherein the at least one compound capable ofreducing the enthalpy of fusion is present in an amount that reduces theenthalpy of fusion of the at least one structuring polymer.
 17. Thecomposition according to claim 16, wherein the reducing the enthalpy offusion is by at least 3 J/g of the at least one structuring polymer. 18.The composition according to claim 16, wherein the at least one compoundcapable of reducing the enthalpy of fusion of the at least onestructuring polymer is additionally capable of reducing the meltingtemperature of the at least one structuring polymer.
 19. The compositionaccording to claim 18, wherein the at least one compound is present inan amount that reduces the melting temperature of the at least onestructuring polymer.
 20. The composition according to claim 19, whereinthe reducing of the melting temperature of the at least one structuringpolymer is at least 3° C.
 21. The composition according to claim 16,wherein the at least one compound capable of reducing the enthalpy offusion and optionally the melting temperature of the at least onestructuring polymer are compounds leading to a macroscopicallyhomogeneous composition and/or which are soluble or dispersible in thefatty phase of the composition.
 22. The composition according to claim16, wherein the at least one compound reduces the enthalpy of fusion ofthe structuring polymer and the melting temperature of the at least onestructuring polymer, and leads to a macroscopically homogeneouscomposition.
 23. The composition according to claim 1, wherein the atleast one compound is octyldodecanol.
 24. The composition according toclaim 23, wherein the amount of the at least one compound capable ofreducing the enthalpy of fusion and optionally the melting temperatureof the at least one structuring polymer ranges from 10 to 20% by weight.25. The composition according to claim 1, wherein the amount of the atleast one compound capable of reducing the enthalpy of fusion of the atleast one structuring polymer ranges from 5 to 25% by weight.
 26. Thecomposition according to claim 1, wherein the mass ratio of the at leastone structuring polymer to the at least one compound capable of reducingthe enthalpy of fusion and optionally the melting temperature of the atleast one structuring polymer ranges from 0.1 to
 50. 27. The compositionaccording to claim 1, which further comprises at least one cosmetic ordermatological active agent.
 28. The composition according to claim 27,wherein the at least one dermatological active agent is selected fromthe group consisting of an essential oil, a vitamin, a moisturizer, asunscreen, a cicatrizing agent, a ceramide, and mixtures thereof. 29.The composition according claim 1, which further comprises at least oneadditive selected from the group consisting of a filler, an antioxidant,a preservative perfume, and mixtures thereof.
 30. The compositionaccording to claim 1, wherein the at least one pigment is selected fromthe group consisting of zinc oxide, iron oxide, titanium oxide, andmixtures thereof.
 31. The composition according to claim 1, whichfurther comprises a dye.
 32. The composition according to claim 1,wherein the composition is a transparent gel or of a transparent stick.33. A mascara, an eyeliner, a foundation, a lipstick, a blusher, amake-up product for the body, an eyeshadow or a face powder, or aconcealer product, which comprises the composition according to claim 1.34. A cosmetic make-up method for the keratinous materials of humanbeings, comprising applying the cosmetic composition according to claim1 to the keratinous material of said human being.
 35. A mascara, aneyeliner, a foundation, a lipstick, a blusher, a make-up product for thebody, an eyeshadow or a face powder, or a concealer product, whichcomprises the composition according to claim
 1. 36. The compositionaccording to claim 1, wherein the at least one compound capable ofreducing the enthalpy of fusion of the at least one structuring polymeris a linear or a branched aliphatic monoalcohol having 12-26 carbonatoms.
 37. The composition according to claim 36, wherein the amount ofthe at least one compound capable of reducing the enthalpy of fusion andoptionally the melting temperature of the at least one structuringpolymer ranges from 10 to 20% by weight.
 38. The composition accordingto claim 1, wherein the amount of the at least one compound capable ofreducing the enthalpy of fusion of the at least one structuring polymerranges from 10 to 20% by weight.
 39. The composition according to claim1, wherein m is from 15 to
 500. 40. The composition according to claim1, wherein m is from 10 to
 100. 41. The composition according to claim1, wherein R¹, R², R³ and R⁴ are methyl groups, X is an (oxy)alkylenegroup containing from 1 to 20 carbon atoms, and Y is an alkylene groupcontaining from 1 to 20 carbon atoms.
 42. The composition according toclaim 41, wherein m is from 15 to
 500. 43. The composition according toclaim 41, wherein m is from 10 to
 100. 44. A make-up structured solidcomposition for the skin, the lips and/or the superficial body growths,comprising at least one pigment in a sufficient quantity for applyingmake-up to the skin, the lips and/or the superficial body growths and aliquid continuous fatty phase comprising at least one structuringpolymer and 5 to 25% by weight of the composition of at least onecompound capable of reducing the enthalpy of fusion of the at least onestructuring polymer which is a linear or a branched aliphaticmonoalcohol having more than 8 carbon atoms but not more than 26 carbonatoms; wherein the at least one structuring polymer has a weight-averagemolecular mass ranging from 500 to 500,000, is a solid at roomtemperature, and is soluble in the liquid fatty phase at a temperatureof 25 to 250° C.; and wherein the at least one structuring polymercomprises at least one moiety of formula (III) or (IV):

in which: 1) R¹, R², R³ and R⁴, which may be identical or different, areselected from the group consisting of an A-substituent, a B-substituent,and a C-substituent: wherein the A-substituent is a linear, branched orcyclic, saturated or unsaturated, C₁ to C₄₀ hydrocarbon, whichoptionally comprises in the chain of the hydrocarbon one or more of anoxygen atom, a sulphur atom, and a nitrogen atom, and optionally ispartially or totally fluorinated; wherein the B-substituent is a C₆ toC₁₀ aryl group, which is optionally substituted with one or more C₁ toC₄ alkyl groups, and wherein the C-substituent is at least onepolyorganosiloxane chain, which optionally comprises in the chain of thepolyorganosiloxane one or more of an oxygen atom, a sulfur atom, and anitrogen atom; 2) the groups X, which may be identical or different,represent a linear or branched C₁ to C₃₀ alkylenediyl group, whichoptionally comprises in the chain of the alkylenediyl group one or moreoxygen atom and/or nitrogen atom; 3) Y is a saturated or unsaturated, C₁to C₅₀ linear or branched divalent alkylene, arylene, cycloalkylene,alkylarylene or arylalkylene group, optionally comprising one or moreoxygen atom, sulfur atom, and/or nitrogen atom, and/or bearing assubstituent one of the following atoms or groups of atoms: fluorine,hydroxyl, C₃ to C₈ cycloalkyl, C₁ to C₄₀ alkyl, C₅ to C₁₀ aryl, phenyloptionally substituted with 1 to 3 C₁ to C₃ alkyl groups, C₁ to C₃hydroxyalkyl and C₁ to C₆ aminoalkyl, or 4) Y represents a groupcorresponding to the formula:

wherein T represents a linear or branched, saturated or unsaturated, C₃to C₂₄ trivalent or tetravalent hydrocarbon group optionally substitutedwith a polyorganosiloxane chain, and optionally comprising one or moreatoms chosen from O, N and S, or T represents a trivalent atom chosenfrom N, P and Al, and R⁵ represents a linear or branched C₁ to C₅₀ alkylgroup or a polyorganosiloxane chain, optionally comprising one or moreester, amide, urethane, thiocarbamate, urea, thiourea and/orsulphonamide groups, which optionally is linked to another chain of thepolymer; and 5) n is an integer ranging from 2 to 500, and m is aninteger ranging from 1 to 1,000, wherein the at least one pigment, theliquid fatty phase, the at least one structuring polymer, and the atleast one compound capable of reducing the enthalpy of fusion of the atleast one structuring polymer form a physiologically acceptable medium.45. The composition according to claim 44, wherein the amount of the atleast one compound capable of reducing the enthalpy of fusion andoptionally the melting temperature of the at least one structuringpolymer ranges from 10 to 20% by weight.